Method for fabricating a nano structure

ABSTRACT

Provided are a nano structure, a fabrication method thereof, and an application device thereof. The method for fabricating a nano structure includes: forming a substrate; forming a plurality of linkers over the substrate; forming a plurality of metal ions over the linkers; and forming one or more metallic nanoparticles over the linkers.

CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority of Korean Patent ApplicationNos. 10-2013-0159761, 10-2013-0159762, and 10-2013-0159763 filed on Dec.19, 2013, which are incorporated herein by reference in their entirety.

BACKGROUND

1. Field

Various embodiments of the present disclosure relate to a nanostructure, a fabrication method thereof, and an application devicethereof.

2. Description of the Related Art

Nano structures have such characteristics as the quantum confinementeffect, the Hall-Petch effect, dropping melting point, resonancephenomenon, excellent carrier mobility and so forth in comparison withconventional bulk and thin firm-type structures. For this reason, thenano structure is being applied to chemical batteries, solar cells,semiconductor devices, chemical sensors, photoelectric devices and thelike.

Nano structures are generally fabricated in either a top-down method ora bottom-up method. The bottom-up method includes a vapor-liquid-solidgrowth method and a liquid growth method. The vapor-liquid-solid growthmethod is based on a catalytic reaction, and includes methods such asthe Thermal Chemical Vapor Deposition (thermal-CVD) method, theMetal-Organic Chemical Vapor Deposition (MOCVD) method, the Pulsed LaserDeposition (PLD) method, and the Atomic Layer Deposition (ALD) method.As for the liquid growth method, a self-assembly technology and ahydrothermal method are being suggested.

According to the conventional bottom-up method, nanoparticles areprepared in advance and then the nanoparticles are attached to asubstrate having a modified surface. However, this method is limitedbecause of nanoparticle size issues that affect the reproducibility andreliability of memory devices in which it is implemented. In otherwords, with the method of fabricating a nano structure by simplyattaching nanoparticles to a substrate, it is likely impossible toimprove memory performance unless nanoparticle synthesis technologymakes remarkable progress.

To overcome this limitation, nanoparticles may be prepared in a top-downmethod such as with lithography. The use of the top-down method,however, requires a great deal of investment in equipment, because ahigh-end lithography facility is needed. Moreover, since the process isquite complicated, the ability to implement it in mass-production islimited. Also, although the etch process is performed using an electronbeam, it is difficult to keep the nanoparticle size under apredetermined level.

SUMMARY

Various embodiments are directed to a nano structure that may be quicklymass-produced through a method that is commercially available andcost-effective, and a fabrication method thereof.

Also, various embodiments are directed to a nano structure havingnanoparticles whose size may be controlled, and a fabrication methodthereof.

Also, various embodiments are directed to a nano structure capable ofsecuring operation stability, reproducibility, and reliability of anapplication device when scaled.

Also, various embodiments are directed to a device including a nanostructure having excellent operation stability, reproducibility, andreliability.

In an embodiment, a method for fabricating a nano structure includes:forming a substrate; forming a plurality of linkers over the substrate;bonding a plurality of metal ions to the linkers; and forming one ormore metallic nanoparticles by growing the metal ions bonded to thelinkers.

The forming of one or more metallic nanoparticles may include: applyingenergy to the metal ions.

The method may further include: bonding at least one between adielectric organic material and an inorganic oxide to a surface of eachof the metallic nanoparticles.

The method may further include: supplying an organic surfactant of oneor more kinds before or during the forming of one or more metallicnanoparticles.

The organic surfactant may be a nitrogen-containing organic material ora sulfur-containing organic material.

The organic surfactant may include a first organic material and a secondorganic material of different kinds, and the first organic material maybe a nitrogen-containing organic material or a sulfur-containing organicmaterial, and the second organic material may be a phase-transfercatalyst-based organic material.

The linkers may be organic monomolecules, and the forming of a pluralityof linkers may include: preparing a linker solution where the linkersare dissolved in a solvent; and forming a self-assembled monomolecularlayer by applying the linker solution to a surface of the substrate.

The linkers may be formed through an Atomic Layer Deposition (ALD)process using a gas containing the linkers.

The forming of a plurality of linkers may include: forming a silanecompound layer through an Atomic Layer Deposition (ALD) process.

The linkers may include at least one functional group selected from thegroup including an amine group, a carboxyl group, and a thiol group, tobe bonded to the metal ions.

The bonding of a plurality of the metal ions to the linkers may include:applying a metal precursor to the linkers.

The bonding of a plurality of the metal ions to the linkers may include:applying a metal precursor solution to a structure where the linkers arebonded, or supplying a gas-phase metal precursor to the structure wherethe linkers are bonded.

The energy may be one or more selected from the group including heatenergy, chemical energy, light energy, vibration energy, ion beamenergy, electron beam energy, and radiation energy.

The metallic nanoparticles may be formed of one selected from the groupincluding metal nanoparticles, metal oxide nanoparticles, metal nitridenanoparticles, metal carbide nanoparticles, and intermetallic compoundnanoparticles, by supplying an element of a different than the metalions during the application of energy to the metal ions.

The energy may be simultaneously applied to all metal ion-bondedregions.

The energy may be selectively or intermittently applied to keep aportion of the metal ions away from being particlized.

The forming of the substrate may include: forming a surface layercapable of being bonded to the linkers on a surface of the substrate.The surface layer may be formed of one or more selected from the groupincluding metals, metal oxides, semiconductors and semiconductor oxides.

The application of energy may be adjusted to control the size or densityof the metallic nanoparticles.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A to 1F are cross-sectional views illustrating a nano structureand a method for fabricating the nano structure in accordance with afirst embodiment of the present disclosure.

FIGS. 2A to 2E are cross-sectional views describing a nano structure anda method for fabricating the nano structure in accordance with a secondembodiment of the present disclosure.

DETAILED DESCRIPTION

Hereinafter, a single electron transistor and a fabrication methodthereof according to embodiments of the present disclosure will bedescribed in detail with reference to the accompanying drawings. Thepresent disclosure may, however, be embodied in different forms andshould not be construed as limited to the embodiments set forth herein.Rather, these embodiments are provided so that this disclosure will bethorough and complete, and will fully convey the scope of the presentdisclosure to those skilled in the art. In addition, the drawings arenot necessarily to scale and, in some instances, proportions may havebeen exaggerated in order to clearly illustrate features of theembodiments. Throughout the disclosure, reference numerals correspond tothe like numbered parts in the various figures and embodiments of thepresent invention.

It should be understood that the meaning of “on” and “over” in thepresent disclosure should be interpreted in the broadest manner suchthat “on” means not only “directly on” but also “on” something withintermediate feature(s) or a layer(s) therebetween, and that “over”means not only directly on but also on something with an intermediatefeature(s) or layer(s) therebetween. It is also noted that in thisspecification, “connected/coupled” refers to one component not onlydirectly coupling another component but also indirectly coupling anothercomponent through an intermediate component. In addition, a singularform may include a plural form, and vice versa, as long as it is notspecifically mentioned.

Unless otherwise mentioned, all terms used herein, including technicalor scientific terms, have the same meanings as understood by thoseskilled in the technical field to which the present disclosure pertains.In the following description, a detailed description of known functionsand configurations will be omitted when it may obscure the subjectmatter of the present disclosure.

Nano Structure and Fabrication Method Thereof in Accordance with a FirstEmbodiment of the Present Invention

FIGS. 1A to 1F are cross-sectional views illustrating a nano structureand a method for fabricating the nano structure in accordance with afirst embodiment of the present disclosure.

In accordance with the first embodiment of the present disclosure, amethod for fabricating a nano structure may include preparing asubstrate 110 (see FIG. 1A); bonding linkers 120A to the substrate 110(see FIG. 1B); bonding metal ions 130 to the linkers 120A (see FIGS. 1Cand 1D); and forming (i.e. growing or reducing) the metal ions 130 intometallic nanoparticles 140 by applying energy (see FIG. 1E). The methodfor fabricating a nano structure may further include supplying adielectric organic material 150 to the structure including the metallicnanoparticles 140 (see FIG. 1F). Even further, the method forfabricating a nano structure may further include supplying organicsurfactants of one or more kinds before the energy is applied, or whileapplying energy.

FIG. 1A shows the prepared substrate 110. Referring to FIG. 1A, thesubstrate 110 may have a surface layer 114 having a functional groupcapable of being bonded to a linker. For example, the substrate 110 maybe a silicon substrate 112 having a silicon oxide (SiO₂) layer as thesurface layer 114.

The substrate 110 may be a semiconductor substrate, a transparentsubstrate, or a flexible substrate. The material, structure, and shapeof the substrate 110 may differ according to the application device.Also, the substrate 110 may serve as a physical support to theconstituent elements of the application device, or the substrate 110 maybe a raw material of the constituent elements.

Non-limiting examples of flexible substrates include a flexible polymersubstrate formed of polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene(PP), triacetyl cellulose (TAC), polyethersulfone (PES),polydimethylsiloxane (PDMS), or a mixture thereof. When a flexiblesubstrate is used, the surface layer 114 of the substrate may be made ofan organic material having a functional group (e.g., —OH functionalgroup) capable of being bonded to the linkers.

When using a semiconductor substrate, the substrate may be an organicsemiconductor, an inorganic semiconductor, or a stacked structurethereof.

Non-limiting examples of inorganic semiconductor substrates includematerials selected from the group including group 4 semiconductors,which include silicon (Si), germanium (Ge) and silicon germanium (SiGe);group 3-5 semiconductors, which include gallium arsenide (GaAs), indiumphosphide (InP) and gallium phosphide (GaP); group 2-6 semiconductors,which include cadmium sulfide (CdS) and zinc telluride (ZnTe); group 4-6semiconductors, which include lead sulfide (PbS); and a stack of two ormore layers made of different materials selected from these materials.From the perspective of crystallography, the inorganic semiconductorsubstrate may be a monocrystalline material, a polycrystalline material,an amorphous material, or a mixture of a crystalline material and anamorphous material. When the inorganic semiconductor substrate is astacked structure, where two or more layers are stacked, each layer maybe a monocrystalline material, a polycrystalline material, an amorphousmaterial, or a mixture of a crystalline material and an amorphousmaterial.

To be specific, the inorganic semiconductor substrate may be asemiconductor substrate including a wafer, such as a silicon (Si)substrate 112, a silicon substrate with a surface oxide layer, or aSilicon On Insulator (SOI) substrate including a wafer.

When using an organic semiconductor substrate, the organic semiconductormay be an n-type organic semiconductor or a p-type organicsemiconductor, which are typically used in the fields of organictransistors, organic solar cells, and organic light emitting diodes(OLED). Non-limiting examples of organic semiconductors includefulleren-derivatives, such as copper-phthalocyanine (CuPc),poly(3-hexylthiophene) (P3HT), pentacene, subphthalocyanines (SubPc),fulleren (C60), [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and[6,6]-phenyl C70-butyric acid methyl ester (PC70BM), and tetrauorotetracyanoquinodimethane (F4-TCNQ). Again, these are non-limitingexamples, and those skilled in the art will appreciate otherpossibilities that would fall within the spirit and scope of the presentinvention.

The surface layer 114 of the substrate 110 may be formed of any materialthat has a functional group capable of being bonded to the linkers. Forexample, the surface layer 114 may be a single layer or a stacked layer,where two or more layers of different materials are stacked. Where thesurface layer 114 is a stacked layer, the dielectric constant of eachlayer may be different.

To be specific, the surface layer 114 of the substrate 110 may be asingle layer of a material selected from the group including an oxide, anitride, an oxynitride, and a silicate, or a stack of two or morelayers, each of which is selected from the group. Non-limiting examplesof the surface layer 114 of the substrate 110 include a single layer ofat least one material selected from the group including a silicon oxide,a hafnium oxide, an aluminum oxide, a zirconium oxide, a barium-titaniumcomposite oxide, an yttrium oxide, a tungsten oxide, a tantalum oxide, azinc oxide, a titanium oxide, a tin oxide, a barium-zirconium compositeoxide, a silicon nitride, a silicon oxynitride, a zirconium silicate, ahafnium silicate, a mixture thereof, and a composite thereof, or a stackof two or more layers, each of which is selected from the group.

The surface layer 114 of the substrate 110 may be a metal thin film. Themetal thin film may have a thickness of about 100 nm or less. Accordingto an embodiment of the present disclosure, the metal thin film may havea thickness of about 1 nm to 100 nm. When the metal thin film isextremely, about 1 nm or less, the uniformity of the thin film maydeteriorate. Non-limiting examples of the material for the metal thinfilm, which is used as the surface layer 114, may include transitionmetals including noble metals, metals, and mixtures thereof. Examples ofthe transition metals include Sc, Y, La, Ac, Ti, Zr, Hf, V, Nb, Ta, Cr,Mo, W, Mn, Te, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, andmixtures thereof, and examples of the metals include Li, Na, K, Rb, Cs,Fr, Be, Mg, Ca, Sr, Ba, Ra, Zn, Cd, Al, Ga, In, Tl, Ge, Sn, Pb, Sb, Bi,Po, and mixtures thereof.

The surface layer 114 may be formed through a thermal oxidation process,a physical deposition process, or a chemical deposition process.Non-limiting examples of the physical deposition process and thechemical deposition process include sputtering, magnetron-sputtering,e-beam evaporation, thermal evaporation, Laser Molecular Beam Epitaxy(L-MBE), a Pulsed Laser Deposition (PLD), vacuum deposition, AtomicLayer Deposition (ALD), and Plasma Enhanced Chemical Vapor Deposition(PECVD).

FIG. 1B shows a linker layer 120 formed on the substrate 110. The linkerlayer 120 may be composed of a plurality of linkers 120A. The linkerlayer 120 may be a self-assembled monomolecular layer bonded to thesurface of the substrate 110.

The linkers 120A may be organic linkers that are chemically bonded to oradsorbed on the surface of the substrate 110 and may chemically bondwith metal ions. Specifically, the linkers 120A may be organic linkershaving both a functional group 122 that is chemically bonded to oradsorbed on the surface layer 114 of the substrate 110 and a functionalgroup 126 that is chemically bonded to metal ions (to be formed later).The chemical bond may include a covalent bond, an ionic bond, or acoordination bond. For example, the bond between metal ions and thelinkers may be an ionic bond between positively charged (or negativelycharged) metal ions and negatively charged (or positively charged)linkers, at least at one end. The bond between the surface layer of thesubstrate 110 and the linkers may be a bond caused by self-assembly ormay be a spontaneous chemical bond between the functional group 122 ofthe linkers and the surface of the substrate.

The linkers 120A may be organic monomolecules that form a self-assembledmonomolecular layer. In other words, the linkers 120A may be organicmonomolecules having both the functional group 122 that is bonded to thesurface layer 114 and a functional group 126 capable of bonding withmetal ions. The linkers 120A may include a chain group 124, whichconnects the functional group 122 with the functional group 126 andenables the formation of a monomolecular layer aligned by Van Der Waalsinteractions.

Self-assembly may be achieved by suitably designing the material of thesubstrate surface and the first functional group 122 of the organicmonomolecule. A set of end groups for materials that are generally knownto be self-assembling may be used.

In a specific non-limiting embodiment, when the surface layer 114 of thesubstrate 110 is made of oxide, nitride, oxynitride, or silicate, theorganic monomolecule that is the linker may be a compound represented bythe following Formula 1.R1-C—R2  (Formula 1)

In Formula 1, R1 represents a functional group that bonds with thesubstrate, C represents a chain group, and R2 represents a functionalgroup that bonds with metal ions. R1 may be one or more functionalgroups selected from the group including acetyl, acetic acid, phosphine,phosphonic acid, alcohol, vinyl, amide, phenyl, amine, acryl, silane,cyan and thiol groups. C is a linear or branched carbon chain having 1to 20 carbon atoms. R2 may be one or more functional groups selectedfrom the group including carboxylic acid, carboxyl, amine, phosphine,phosphonic acid and thiol groups.

In a non-limiting embodiment, the organic monomolecule that is thelinker 120A may be one or more selected from a group includingoctyltrichlorosilane (OTS), hexamethyldisilazane (HMDS),octadecyltrichlorosilane (ODTS), (3-aminopropyl)trimethoxysilane (APS),(3-aminopropyl)triethoxysilane, N-(3-aminopropyl)-dimethylethoxysilane(APDMES), perfluorodecyltrichlorosilane (PFS),mercaptopropyltrimethoxysilane (MPTMS),N-(2-aminoethyl)-3aminopropyltrymethoxysilane,(3-trimethoxysilylpropyl)diethylenetriamine, octadecyltrimethoxysilane(OTMS), (heptadecafluoro-1,1,2,2-tetrahydrodecyl)trichlorosilane (FDTS),dichlorodimethylsilane (DDMS), N-(trimethoxysilylpropyl)ethylenediaminetriacetic acid, hexadecanethiol (HDT), and epoxyhexyltriethoxysilane.

In terms of ensuring stable isolation between the nanoparticles and thesubstrate, the organic monomolecule that is the linker may include analkane chain group, particularly an alkane chain group having 3 to 20carbon atoms, and may further include an oxygen-containing moiety.Examples of the oxygen-containing moiety include ethylene glycol(—O—CH₂—CH₂—), carboxylic acid (—COOH), alcohol (—OH), ether (—O—),ester (—COO—), ketone (—CO—), aldehyde (—COH) and/or amide (—NH—CO—),etc.

Attachment of the linkers 120A may be performed by bringing thesubstrate 110 into contact with a solution of linkers 120A in a solvent.The solvent that is used to form the linker solution may be any solventthat can dissolve the linkers and be easily removed by volatilization.As is known in the art, when the linker contains a silane group, waterfor promoting hydrolysis may be added to the linker solution. Thecontact between the substrate and the linker solution may be performedusing any known method to form a self-assembled monomolecular layer on asubstrate. In a non-limiting embodiment, the contact between the linkersolution and the substrate may be performed using a dipping, microcontact printing, spin-coating, roll coating, screen coating, spraycoating, spin casting, flow coating, screen printing, ink jet coating ordrop casting method.

When metal ions are fixed to the substrate by the linkers 120A, thereare advantages in that damage to the surface layer 114 of the substratemay be prevented, and a uniformly distributed metal ion layer may beformed by self-assembly. Additionally, nanoparticles prepared byapplication of energy may be stably fixed.

The linkers may include functional groups that chemically bond withmetal ions. The surface of the substrate 110 may be modified to form afunctional group (linker), and then a metal precursor may be supplied tothe surface-modified substrate so that metal ions may bond with thefunctional group. The functional group may be one or more selected fromthe group including carboxylic acid, carboxyl, amine, phosphine,phosphonic acid and thiol groups. Formation of the functional group onthe substrate surface may be performed using any method. Specificexamples of the method for forming the functional group on the substratesurface include plasma modification, chemical modification, and vapordeposition (application) of a compound having a functional group.Modification of the substrate surface may be performed by vapordeposition (application of a compound having a functional group) toprevent surface layer impurity introduction, quality deterioration, anddamage.

In a specific non-limiting embodiment, when the surface layer 114 of thesubstrate 110 is formed of an oxide, a nitride, an oxynitride or asilicate, a functional group (linker) may be formed by a silane compoundlayer on the substrate 110.

The silane compound layer may be made of an alkoxy silane compoundhaving one or more functional groups selected from a group includingcarboxylic acid, carboxyl, amine, phosphine, phosphonic acid and thiolgroups.

The silane compound may be represented by the following Formula 2:R¹ _(n)(R²)_(3-n)Si—R  (Formula 2)

In Formula 2, R¹ is hydrogen, a carboxylic acid group, a carboxyl group,an amine group, a phosphine group, a phosphonic acid group, a thiolgroup, or a linear or branched alkyl group having 1 to 10 carbon atoms;R² is a linear or branched alkyl group having 1 to 10 carbon atoms; R isa linear or branched alkyl group having 1 to 10 carbon atoms; the alkylgroup in R may be substituted with one or more selected from a groupincluding carboxylic acid, carboxyl, amine, phosphine, phosphonic acidand thiol groups; the alkyl group in R¹ and the alkyl group in R² mayeach be independently substituted with one or more selected from a groupincluding the halogens, carboxylic acid, carboxyl, amine, phosphine,phosphonic acid and thiol groups; and n is 0, 1 or 2.

The silane compound may be represented by one of the following Formulas3 to 5:(R³)₃Si—R⁴—SH  (Formula 3)(R³)₃Si—R⁴—COOH  (Formula 4)(R³)₃Si—R⁴—NH₂  (Formula 5)

In the Formula 3, 4, and 5, R³ groups are each independently an alkoxyor alkyl group, and one or more R³ groups are an alkoxy group; and R⁴ isa divalent hydrocarbon group having 1 to 20 carbon atoms. R³ groups inFormulas 3, 4 or 5 may be the same or different and may each beindependently an alkoxy group, such as methoxy, ethoxy or propoxy, or analkyl group; and R⁴ may be a divalent hydrocarbon group having 1 to 20carbon atoms, such as —CH₂—, —CH₂—CH₂—, —CH₂—CH₂—CH₂—, —CH₂—CH(CH₃)—CH₂—or —CH₂—CH₂—CH(CH₃)—.

Non-limiting examples of the carboxysilane compound includemethyldiacetoxysilane, 1,3-dimethyl-1,3-diacetoxydisiloxane,1,2-dimethyl-1,2-diacetoxydisilane,1,3-dimethyl-1,3-dipropionoxydisilamethane, and1,3-diethyl-1,3-diacetoxydisilamethane. Non-limiting examples of theaminosilane compound includeN-(2-aminoethyl)aminopropyltri(methoxy)silane,N-(2-aminoethyl)aminopropyltri(ethoxy)silane,N-(2-aminoethyl)aminopropylmethyldi(methoxy)silane,N-(2-aminoethyl)aminopropylmethyldi(ethoxy)silane,3-aminopropyltri(methoxy)silane, 3-aminopropyltri(ethoxy)silane,3-aminopropylmethyldi(methoxy)silane, and3-aminopropylmethyldi(ethoxy)silane. Non-limiting examples of themercaptosilane compound include mercaptopropyltrimethoxysilane,mercaptopropyltriethoxysilane, mercaptoethyltrimethoxysilane, andmercaptoethyltriethoxysilane.

The above-described silane compound may be applied to or deposited onthe surface of the substrate 110 to form a functional group (afunctional group resulting from a silane compound layer). The silanecompound layer may be formed by applying and drying a silane compoundsolution. Alternatively, the silane compound may be deposited bysupplying a gaseous silane compound to the substrate surface.

As the silane compound functional group will react with a metalprecursor (supplied later) to fix metal ions to the substrate, it ispreferred to form a uniform silane compound layer where the functionalgroups are uniformly exposed to the surface. The silane compound layermay be formed by atomic layer deposition (ALD).

The above-described silane compounds having a functional group(particularly the silane compound of Formulas 2, 3, and 4) may belong tothe above-described self-assembly molecule group. Specifically, (R³)₃Simay correspond to the functional group that is bonded to the substratesurface, R⁴ may correspond to the chain group, and R (R in formula 2)such as —SH, —COOH or —NH₂ may correspond to the functional group thatbonds with metal ions. The silane composed layer may be a monomolecularlayer formed of the silane compound.

FIG. 1C shows metal ions 130 bonded to the linkers 120A. The metal ions130 may be bonded to the functional group 126 of the linkers 120A.

The metal ions 130 may be formed by supplying a metal precursor to thesubstrate (having the linkers formed thereon). Specifically, the metalions 130 may be formed by applying (or impregnating) a metal precursorsolution to the substrate or applying a gaseous metal precursor to thesubstrate.

The metal precursor may be designed in view of the material of thedesired nanoparticles. For example, the metal precursor may beprecursors of one or more metals selected from a group includingtransition metals, post-transition metals, and metalloids. In anon-limiting embodiment, the transition metal precursor may be atransition metal salt. Specifically, the transition metal may be one ormore selected from a group including Au, Ag, Ru, Pd and Pt, and thetransition metal salt may be selected from a group including halides,chalcogenides, hydrochlorides, nitrates, sulfates, acetates or ammoniumsalts or the transition metal. When the transition metal of thetransition metal precursor is Au, examples of the transition metalprecursor include, but are not limited to, HAuCl₄, AuCl, AuCl₃, Au₄Cl₃,KAuCl₄, NaAuCl₄, NaAuBr₄, AuBr₃, AuBr, AuF₃, AuF₅, AuI, AuI₃, KAu(CN)₂,Au₂O₃, Au₂S, Au₂S₃, AuSe, Au₂Se₃, and the like.

The metal ions 130 that are bonded (attached) to the substrate by thelinkers 120A may be ions of one or more metals (elements) selected froma group including transition metals, post-transition metals, andmetalloids. Depending on the kind of metal precursor, the metal ions 130may be the above-described metal ions themselves or monomolecular ionsincluding the above-described metals. Metal ions themselves may bebonded to the functional groups 126 of the organic monomolecules(linkers) (see FIG. 1C), or metal-containing monomolecular ions may bebonded to the second functional groups 126 of organic monomolecules (seeFIG. 1D). Metal-containing monomolecular ions may be ions originatingfrom the metal precursor (ions resulting from the reaction between theorganic monomolecules and the functional groups).

FIG. 1E shows metallic nanoparticles 140 formed by the reduction andgrowth of the metal ions 130 by application of energy. The metallicnanoparticles 140 may be formed on the substrate 110 by the linkers120A.

Advanced technology enables the synthesis of very fine nanoparticlesfrom tens to hundreds of atoms, but in view of thermodynamics,synthesized nanoparticles may not have a uniform particle sizedistribution and the difference in size between the nanoparticles mayincrease as the size of the reaction field during synthesis increases.In addition, a method of preparing nanoparticles by etching using atop-down process enables the preparation of particles having a size ofabout 20 nm or less by advanced lithography, but it is difficult toapply commercially because the process is complicated and requiresprecise control.

However, in a preparation method according to an embodiment of thepresent disclosure, nanoparticles are prepared directly in a very smallreaction field corresponding to the surface region of the substrate, andthus nanoparticles having a very uniform and finely controlled size maybe prepared at high density. Because nanoparticles are prepared byfixing metal ions to the substrate by the linkers and then applyingenergy to the metal ions, the nanoparticles may be produced quickly in asimple, easy and cost-effective manner. Further, because nucleation andgrowth (formation of nanoparticles) are induced by application of energyin a state where metal atoms (ions) are fixed to the substrate by thelinkers, the migration of the metal atoms (ions) may be uniformlycontrolled resulting in the formation of more uniform and finenanoparticles. The metal material to be used for nucleation and growthto form nanoparticles may be supplied only by the metal atoms (ions)bonded to the linkers. In other words, the supply of material used toform nanoparticles comes from the diffusion of the metal atoms (ions)bonded to the linkers. Due to bonding of the metal atoms (ions) to thelinkers, the metal atoms (ions) have difficulty migrating beyond apredetermined distance to participate in nucleation and growth, and thusthe reaction field of each nanoparticle may be limited to around thenucleus. Thus, nanoparticles having a more uniform and finer size may beformed on the substrate at high density and the separation distancebetween the formed nanoparticles may also be uniform. In addition,bonding of the metallic nanoparticles to the linkers is maintained, andthus the nanoparticles may be stably fixed to the substrate by thelinkers. Also, the separation distance between the nanoparticles maycorrespond to the diffusion distance of the metal atoms that participatein the nucleation and growth of the nanoparticles.

Energy that is applied to form the nanoparticles may be one or moreselected from among heat energy, chemical energy, light energy,vibration energy, ion beam energy, electron beam energy, and radiationenergy.

Thermal energy may include Joule heat and may be applied directly orindirectly. Direct application of thermal energy may be performed in astate in which a heat source and the substrate having metal ions fixedthereto come into physical contact with each other. Indirect applicationof thermal energy may be performed in a state in which a heat source andthe substrate having metal ions fixed thereto do not come into physicalcontact with each other. Non-limiting examples of direct applicationinclude a method of placing a heating element, which generates Jouleheat by the flow of electric current, beneath the substrate andtransferring thermal energy to the metal ions through the substrate.Non-limiting examples of indirect application include using aconventional heat-treatment furnace including a space in which an object(such as a tube) to be heat-treated is placed, a heat insulationmaterial that surrounds the space to prevent heat loss, and a heatingelement placed inside the heat insulation material. A non-limitingexample of indirect heat application is seen in the method of placing aheating element at a predetermined distance above the substrate, wherethe metal ions are fixed, and transferring thermal energy to the metalions through a fluid (including air) present between the substrate andthe heating element.

Light energy may include light having a wavelength ranging from extremeultraviolet to near-infrared, and application of light energy mayinclude irradiation with light. In a non-limiting embodiment, a lightsource may be placed above the substrate, having the metal ions fixedthereto, at a predetermined distance from the metal ions, and light fromthe light source may be irradiated onto the metal ions.

Vibration energy may include microwaves and/or ultrasonic waves.Application of vibration energy may include irradiation with microwavesand/or ultrasonic waves. In a non-limiting embodiment, a microwaveand/or ultrasonic wave source may be placed above the substrate, havingthe metal ions fixed thereto, at a predetermined distance from the metalions, and microwaves and/or ultrasonic waves from the source may beirradiated onto the metal ions.

Radiation energy may include one or more selected from a group includingα rays, β rays and γ rays and may be β rays and/or γ rays in terms ofreduction of the metal ions. In a non-limiting embodiment, a radiationsource may be placed above the substrate, having the metal ions fixedthereto, at a predetermined distance from the metal ions, and radiationfrom the source may be irradiated onto the metal ions.

Energy may be kinetic energy of a particle beam, and the particle beammay include an ion beam and/or an electron beam. The ions of the beammay be negatively charged. In a non-limiting embodiment, an ion orelectron source may be placed above the substrate, having the metal ionsfixed thereto, at a predetermined distance from the metal ions, and anion beam and/or electron beams may be applied to the metal ions using anaccelerating element that provides an electric field (magnetic field)that accelerates ions or electrons in the direction of the metal ions.

Chemical energy is the Gibbs free energy difference between before andafter a chemical reaction, and the chemical energy may include reductionenergy. Chemical energy may include the energy of a reduction reactionwith a reducing agent and may mean the energy of a reduction reaction inwhich the metal ions are reduced by the reducing agent. In anon-limiting embodiment, application of chemical energy may be areduction reaction in which the reducing agent is brought into contactwith the substrate having the metal ions fixed thereto. The reducingagent may be supplied in the liquid or gaseous state.

In a fabrication method according to an embodiment of presentdisclosure, application of energy may include simultaneously orsequentially applying two or more selected from among heat energy,chemical energy, light energy, vibration energy, ion beam energy,electron beam energy, and radiation energy.

In a specific embodiment of simultaneous application, application ofheat may be performed simultaneously with application of a particlebeam. The particles of the particle beam may be heated by heat energy.In another specific embodiment of simultaneous application, applicationof heat may be performed simultaneously with application of a reducingagent. In still another embodiment of simultaneous application,application of a particle beam may be performed simultaneously withapplication of infrared rays or with application of microwaves.

Sequential application may mean that one kind of energy is appliedfollowed by application of another kind of energy. It may also mean thatdifferent kinds of energy are continuously or discontinuously applied tothe metal ions. It is preferable that reduction of the metal ions fixedto the substrate by the linkers be performed before formation ofnanoparticles, and thus in a specific embodiment of sequentialapplication, heat may be applied after addition of a reducing agent orafter application of a positively charged particle beam.

In a non-limiting practical embodiment, application of energy may beperformed using a rapid thermal processing (RTP) system including atungsten-halogen lamp, and the rapid thermal processing may be performedat a heating rate of 50 to 150° C./sec. Also, rapid thermal processingmay be performed in a reducing atmosphere or an inert gas atmosphere.

In a non-limiting practical embodiment, application of energy may beperformed by bringing a solution of a reducing agent into contact withthe metal ions followed by thermal processing using the rapid thermalprocessing system in a reducing atmosphere or an inert gas atmosphere.

In a non-limiting practical embodiment, application of energy may beperformed by generating an electron beam from an electron beam generatorin a vacuum chamber and accelerating the generated electron beam to themetal ions. The electron beam generator may be a square type or a lineargun type. The electron beam may be produced by generating plasma fromthe electron beam generator and extracting electrons from the plasmausing a shielding membrane. In addition, a heating element may beprovided on a holder for supporting the substrate in the vacuum chamber,and heat energy may be applied to the substrate by this heating elementbefore, during and/or after application of the electron beam.

When the desired nanoparticles are metal nanoparticles, the metalnanoparticles may be prepared in situ by application of energy asdescribed above. When the nanoparticles to be prepared are not metalnanoparticles, but are metal compound nanoparticles, the metal compoundnanoparticles may be prepared by supplying an element different from themetal ions during or after application of the above-described energy.Specifically, the metal compound nanoparticles may include metal oxidenanoparticles, metal nitride nanoparticles, metal carbide nanoparticlesor intermetallic compound nanoparticles. More specifically, the metalcompound nanoparticles may be prepared by supplying a different elementin the gaseous or liquid state during or after application of theabove-described energy. In a specific embodiment, metal oxidenanoparticles in place or metal nanoparticles may be prepared bysupplying an oxygen source including oxygen gas during application ofenergy. In addition, metal nitride nanoparticles in place of metalnanoparticles may be prepared by supplying a nitrogen source includingnitrogen gas during application of energy. Metal carbide nanoparticlesmay be prepared by supplying a carbon source, including C₁-C₁₀hydrocarbon gas during application of energy, and intermetallic compoundnanoparticles may be prepared by supplying a precursor gas containing adifferent element, which provides an intermetallic compound, duringapplication of energy. Specifically, the intermetallic compoundnanoparticles may be prepared by carbonizing, oxidizing, nitrifying oralloying the metal nanoparticles prepared by application of theabove-described energy.

The density of nanoparticles (the number of nanoparticles per unitsurface area of the channel region) and the particle size and particlesize distribution may be controlled by the energy applicationconditions, including the kind, magnitude, temperature, and duration ofenergy application.

To be specific, nanoparticles having an average particle diameter ofabout 0.5 nm to 3 nm may be fabricated by applying energy. In this case,uniform nanoparticles may be prepared with a particle radius standarddeviation of about ±20% or less, and highly dense nanoparticles having ananoparticle density (which is the number of the nanoparticles per unitarea) of about 10¹³ to 10¹⁵/cm² may be prepared.

According to an embodiment, when the applied energy is electron beam,the electron beam may be irradiated at a dose of about 0.1 KGy to 100KGy. With the irradiation dose of the electron beam, nanoparticleshaving an average particle diameter of about 2 to 3 nm may be prepared,and the nanoparticles may have a particle radius standard deviation ofabout ±20% or less. The prepared nanoparticle density (which is thenumber of the nanoparticles per unit area) may range from about 10¹³ to10¹⁵/cm², and specifically, the nanoparticle density may range fromabout 0.1×10¹⁴ to 10×10¹⁴/cm².

According to smother embodiment, when the applied energy is an electronbeam, the electron beam may be irradiated at a dose of about 100 μGy to50 KGy. With the irradiation dose of the electron beam, nanoparticleshaving an average particle diameter of about 1.3 to 1.9 nm may beprepared, and the nanoparticles may have a particle radius standarddeviation of about ±20% or less. The prepared nanoparticle density(which is the number of the nanoparticles per unit area) may range fromabout 10¹³ to 10¹⁵/cm², and specifically, the nanoparticle density mayrange from about 0.2×10¹⁴ to 20×10¹⁴/cm².

According to another embodiment, when the applied energy is electronbeam, the electron beam may be irradiated at a dose of about 1 μGy to 10KGy. With the irradiation dose of electron beam, nanoparticles having anaverage particle diameter of about 0.5 to 1.2 nm may be prepared, andthe nanoparticles may have a particle radius standard deviation of about±20% or less. The prepared nanoparticle density (which is the number ofthe nanoparticles per unit area) may range from about 10¹³ to 10¹⁵/cm²,and specifically, the nanoparticle density may range from about 0.2×10¹⁴to 30×10¹⁴/cm².

According to another embodiment, when the applied energy is heat energy,nanoparticles having an average particle diameter of about 2 to 3 nm maybe prepared by performing a heat treatment in a reducing atmosphere at atemperature of about 100 to 500° C. for about 0.5 to 2 hours or bysupplying a reducing agent to the metal ions bonded to the linkers andperforming a heat treatment in an inert gas atmosphere at a temperatureof about 200 to 400° C. for about 0.5 to 2 hours. The preparednanoparticles may have a particle radius standard deviation of about±20% or less. The prepared nanoparticle density (which is the number ofthe nanoparticles per unit area) may range from about 10¹³ to 10¹⁵/cm²,and specifically, the nanoparticle density may range from about 0.1×10¹⁴to 10×10¹⁴/cm².

According to another embodiment, when the applied energy is heat energy,nanoparticles having an average particle diameter of about 1.3 to 1.9 nmmay be prepared by performing a heat treatment in a reducing atmosphereat a temperature of about 200 to 400° C. for about 0.5 to 2 hours or bysupplying a reducing agent to the metal ions bonded to the linkers andperforming a heat treatment in an inert gas atmosphere at a temperatureof about 100 to 300° C. for about 0.5 to 2 hours. The preparednanoparticles may have a particle radius standard deviation of about±20% or less. The prepared nanoparticle density (which is the number ofthe nanoparticles per unit area) may range from about 10¹³ to 10¹⁵/cm²,and specifically, the nanoparticle density may range from about 0.2×10¹⁴to 20×10¹⁴/cm².

According to another embodiment, when the applied energy is heat energy,nanoparticles having an average particle diameter of about 0.5 to 1.2 nmmay be prepared by performing a heat treatment in a reducing atmosphereat a temperature of about 200 to 400° C. for about 0.2 to 1 hour or bysupplying a reducing agent to the metal ions bonded to the linkers andperforming a heat treatment in an inert gas atmosphere at a temperatureof about 100 to 300° C. for about 0.2 to 1 hour. The preparednanoparticles may have a particle radius standard deviation of about±20% or less. The prepared nanoparticle density (which is the number ofthe nanoparticles per unit area) may range from about 10¹³ to 10¹⁵/cm²,and specifically, the nanoparticle density may range from about 0.2×10¹⁴to 30×10¹⁴/cm².

According to another embodiment, when the applied energy is chemicalenergy, nanoparticles having an average particle diameter of about 2 to3 nm may be prepared by performing a chemical reaction with a reducingagent at a reaction temperature of about 20 to 40° C. for about 0.5 to 2hours. The prepared nanoparticles may have a particle radius standarddeviation of about ±20% or less. The prepared nanoparticle density(which is the number of the nanoparticles per unit area) may range fromabout 10¹³ to 10¹⁵/cm², and specifically, the nanoparticle density mayrange from about 0.1×10¹⁴ to 10×10¹⁴/cm².

According to another embodiment, when the applied energy is chemicalenergy, nanoparticles having an average particle diameter of about 1.3to 1.9 nm may be prepared by performing a chemical reaction induced by areducing agent at a reaction temperature of about −25 to 5° C. for about0.5 to 2 hours. The prepared nanoparticles may have a particle radiusstandard deviation of about ±20% or less. The prepared nanoparticledensity (which is the number of the nanoparticles per unit area) mayrange from about 10¹³ to 10¹⁵/cm², and specifically, the nanoparticledensity may range from about 0.2×10¹⁴ to 20×10¹⁴/cm².

According to another embodiment, when the applied energy is chemicalenergy, nanoparticles having an average particle diameter of about 0.5to 1.2 nm may be prepared by performing a chemical reaction induced by areducing agent at a reaction temperature of about −25 to 5° C. for about0.2 to 1 hour. The prepared nanoparticles may have a particle radiusstandard deviation of about ±20% or less. The prepared nanoparticledensity (which is the number of the nanoparticles per unit area) mayrange from about 10¹³ to 10¹⁵/cm², and specifically, the nanoparticledensity may range from about 0.2×10¹⁴ to 30×10¹⁴/cm².

As described above, nanoparticles may be grown by applying heat energyand/or chemical energy in a reducing atmosphere. When heat energy isapplied in a reducing atmosphere, the reducing atmosphere may containhydrogen. In a specific embodiment, the reducing atmosphere may be aninert gas containing about 1 to 5% hydrogen. In terms of providinguniform reduction, heat energy may be applied in an atmosphere in whicha reducing gas flows. In a specific embodiment, the atmosphere may havereducing gas flowing at a rate of about 10 to 100 cc/min. When chemicalenergy and heat energy are to be sequentially applied, a reducing agentmay be brought into contact with the metal ions, followed by applicationof heat energy in an inert atmosphere. The reducing agent may be anycompound that reduces the metal ions into a metal. When chemical energyis applied by addition of the reducing agent, transition metalnanoparticles may also be formed by a reduction reaction. Whennanoparticles are to be formed from the metal ions by a reductionreaction, the reduction reaction should occur very rapidly and uniformlythroughout the channel region so that transition metal particles havinga more uniform size may be formed. A strong reducing agent may be used,and in a preferred embodiment, the reducing agent may be NaBH₄, KBH₄,N₂H₄H₂O, N₂H₄, LiAlH₄, HCHO, CH₃CHO, or a mixture of two or morethereof. Also, when chemical energy is applied, the size of thenanoparticles may be controlled by adjusting the chemical reactiontemperature and controlling the nucleation rate and the growth of thenanoparticles when a strong reducing agent, as described above, is used.The contact between the metal ions bonded to the linkers and thereducing agent may be achieved either by applying a solution of thereducing agent to the metal ion bonded region, or by impregnating thesubstrate with a solution of the reducing agent, or by supplying thereducing agent in the gaseous phase to the substrate. In a specificnon-limiting embodiment, the contact between the reducing agent and themetal ions may be performed at room temperature for about 1 to 12 hours.

As described above, the nucleation and growth of transition metalnanoparticles may be controlled by one or more factors selected fromamong the kind, magnitude, and duration of the applied energy.

Meanwhile, it is possible to prepare not only metallic nanoparticles butalso metal oxide nanoparticles, metal nitride nanoparticles, metalcarbide nanoparticles, or intermetallic compound nanoparticles bysupplying a heterogeneous atom source while energy is applied or afterenergy is applied to change metallic nanoparticles into metalliccompound nanoparticles.

In a fabrication method according to an embodiment of the presentdisclosure, i) the size of nanoparticles may be controlled by supplyingan organic surfactant that is bonded to or adsorbed on the metal ions,followed by application of energy. Otherwise, ii) the size ofnanoparticles may be controlled during the growth thereof by supplyingan organic surfactant that is to be bonded to or adsorbed on the metalions during application of energy. This supply of the organic surfactantmay be optionally performed during the fabrication process. Instead of asingle organic surfactant that is applied before or during applicationof energy, a plurality of organic surfactants may be used.

To more effectively inhibit the mass transfer of the metal ions, a firstorganic material and a second organic material that are different fromeach other may be used as the surfactant.

The first organic material may be a nitrogen- or sulfur-containingorganic compound. For example, the sulfur-containing organic materialmay include a linear or branched hydrocarbon compound having a thiolgroup at one end. In a specific example, the sulfur-containing organiccompound may be one or more selected from a group including HS—C_(n)—CH₃(n: an integer ranging from 2 to 20), n-dodecyl mercaptan, methylmercaptan, ethyl mercaptan, butyl mercaptan, ethylhexyl mercaptan,isooctyl mercaptan, tert-dodecyl mercaptan, thioglycolacetic acid,mercaptopropionic acid, mercaptoethanol, mercaptopropanol,mercaptobutanol, mercaptohexanol and octyl thioglycolate.

The second organic material may be a phase-transfer catalyst-basedorganic compound, for example, quaternary ammonium or a phosphoniumsalt. More specifically, the second organic surfactant may be one ormore selected from a group including tetraocylyammonium bromide,tetraethylammonium, tetra-n-butylammonium bromide, tetramethylammoniumchloride, and tetrabutylammonium fluoride.

The organic surfactant that is applied before or during application ofenergy may be bonded to or adsorbed on the nuclei of metal ions or themetal ions bonded to the linkers, and the nucleation and growth ofnanoparticles by energy applied may be controlled by the organicsurfactant that is bonded to or adsorbed on the metal ions. This organicsurfactant makes it possible to inhibit the mass transfer of the metalions during application of energy to thereby form more uniform and finernanoparticles. Because the metal ions bond with the organic surfactant,these metal ions require higher activation energy compared to when theydiffuse in order to participate in nucleation or growth, or thediffusion thereof is physically inhibited by the organic surfactant.Thus, the diffusion of the metal atoms (ions) may be slower and thenumber of metal atoms (ions) that participate in the growth of nucleimay be decreased.

The process of applying energy in the presence of the organic surfactantmay include, before application of energy, applying a solution of theorganic surfactant to the channel region (i.e., the substrate surfacehaving the metal ions bonded thereto by the linkers) or supplying theorganic surfactant in the gaseous state to the channel region.Alternatively, it may include, together with application of energy,applying a solution of the organic surfactant to the channel regionhaving the metal ions formed therein or supplying the organic materialin the gaseous state to the channel region to bond or adsorb the organicsurfactant to the metal nuclei. Alternatively, it may include, duringapplication of energy, applying a solution of the organic surfactant tothe channel region having the metal ions formed therein or supplying theorganic material in the gaseous state to the channel region to bond oradsorb the organic surfactant to the metal nuclei. Alternatively, it mayinclude, after application of energy for a predetermined period of timeand then pausing application of energy, applying a solution of theorganic surfactant to the channel region having the metal ions formedtherein or supplying the organic material in the gaseous state to thechannel region to bond or adsorb the organic surfactant to the metalnuclei, followed by re-application of energy.

In a fabrication method according to a first embodiment of the presentdisclosure, energy may be applied to the entire area or a portion of theregion having the metal ions bonded thereto. When energy is applied to aportion of the region, energy may be irradiated in a spot, line orpredetermined plane shape. In a non-limiting embodiment, energy may beapplied (irradiated) in spots while the entire metal ion-bonded regionmay be scanned. Application of energy to a portion of the metalion-bonded region may include not only irradiating energy in a spot,line or plane shape while the metal ion-bonded region is entirelyscanned, but also includes where energy is applied (irradiated) only toa portion of the metal ion-bonded region. As described above, a patternof nanoparticles may be formed by applying energy to a portion of thechannel region. In other words, application (irradiation) of energy to aportion of the channel region makes it possible to form a pattern ofnanoparticles.

FIG. 1F shows a dielectric organic material 150 bonded to the metallicnanoparticles 140 grown by application of energy. The dielectric organicmaterial 150 may be in a state in which it coats the surface of themetallic nanoparticles 140 or fills the gaps between the metallicnanoparticles 140. The dielectric organic material 150 may provideisolation between the nanoparticles to more reliably prevent the flow ofcurrent between nanoparticles.

If a sufficient amount of the organic surfactant was supplied in thepreceding action, that is, if the organic surfactant that is appliedbefore or during application of energy remains on the surface of thegrown nanoparticles to provide sufficient isolation between the grownnanoparticles, the dielectric organic material 150 does not need to beadded to the surface of the grown nanoparticles 140. In other words,because whether the organic material is to be used before or duringapplication of energy (or the supply or kind of organic material, etc.)is determined according to the size of nanoparticles to be formed, theformation of the dielectric organic material 150 after the nanoparticles140 have been grown is optional.

Supply of the dielectric organic material 150 may be performed byapplying a solution of the dielectric organic material to thenanoparticle layer formed by application of energy, and then drying theapplied solution, thereby filling the dielectric organic material intothe gaps between the nanoparticles. This may provide a structure inwhich the nanoparticles are embedded in a dielectric matrix made of thedielectric organic material. The dielectric organic material that isused in the present disclosure may be any conventional dielectricmaterial that is used to form dielectric layers in conventionalorganic-based electronic devices. Specific examples of the dielectricorganic material include, but are not limited to, benzocyclobutene(BCB), acrylic compounds, polyimide, polymethylmethacrylate (PMMA),polypropylene, fluorinated compounds (e.g., CYTOPTM), polyvinyl alcohol,polyvinyl phenol, polyethylene terephthalate, poly-p-xylylene,cyanopulluane (CYMM) and polymethylstyrene.

The dielectric organic material 150 may be a substance thatspontaneously bonds with a metal. In other words, after the formation ofnanoparticles by application of energy, the dielectric organic materialmay be bonded to the metal of the nanoparticles (i.e., the metal of themetal ions attached to the substrate by the linkers), either by applyingto the channel region a solution of the dielectric organic material thatspontaneously bonds with the metal of the metal ions attached to thesubstrate by linkers, or by supplying the dielectric organic material inthe gaseous state to the channel region, thereby forming compositenanoparticles having a core-shell structure including nanoparticle coresand dielectric shells. According to this method, a very uniformdielectric layer may be formed on fine nanoparticles, and more reliableisolation between the nanoparticles may be ensured.

The dielectric organic material 150 that is used in the presentdisclosure may be any dielectric material having a functional group thatbonds with the metal contained in the nanoparticles. In a specificembodiment, the dielectric organic material that spontaneously bondswith the metal contained in the nanoparticles may include, at one end, afunctional group such as a thiol group (—SH), a carboxyl group (—COOH)and/or an amine group (—NH₂) that may spontaneously form a chemical bondwith the metal contained in the nanoparticles, and at the other end, afunctional group such as a methyl group that does not react with themetal contained in the nanoparticles, and as the backbone, an alkanechain that enables the formation of a uniform dielectric layer. Thethickness of the dielectric layer (shell) may be controlled by thecarbon number of the alkane chain, and the dielectric organic materialmay have a C₃-C₂₀ alkane chain.

As an example, when the layer formed of the metallic nanoparticles 140and the dielectric organic material 150 is applied to a floating gate ofa flash memory cell, the weight ratio between the metallic nanoparticlesand the dielectric organic material in the floating gate may be about1:0.5 to 10. This weight ratio between the metallic nanoparticles andthe dielectric organic material may stably prevent current from flowingthrough the nanoparticles and provide the floating gate with physicalstability. This weight ratio between the nanoparticles and thedielectric organic material may be controlled by the amount ofdielectric organic material that is supplied to the substrate having thenanoparticles formed therein. In addition, when a dielectric organicmaterial spontaneously bonds with the surface of the nanoparticles, theweight ratio between the nanoparticles and the dielectric material mayalso be controlled by the carbon number of the alkane chain of thedielectric organic material, as described above.

In order to more securely fix the nanoparticles 140 having thedielectric organic material 150 formed thereon, a layer of an inorganicoxide may additionally be formed. The inorganic oxide layer may beformed directly on the nanoparticles without the dielectric organicmaterial. The organic oxide layer may be formed by a conventional vapordeposition or a liquid dipping method.

Referring to FIG. 1F, the nano structure formed through the fabricationmethod in accordance with the first embodiment of the present inventionis described in detail.

Referring to FIG. 1F, the nano structure in accordance with the firstembodiment of the present invention may include a substrate 110, linkers120A formed over the substrate 110, and metallic nanoparticles 140 thatare grown from metal ions bonded to the linkers 120A. The nano structuremay further include a dielectric organic material 150 bonded to thesurface of the metallic nanoparticles 140.

The substrate 110 may include a surface layer 114 having a functionalgroup capable of being bonded to the linkers 120A. The surface layer 114may include an oxide layer. To be specific, non-limiting examples of thesurface layer 114 of the substrate 110 may be a layer of at least onematerial selected from the group including a silicon oxide, a hafniumoxide, an aluminum oxide, a zirconium oxide, a barium-titanium compositeoxide, an yttrium oxide, a tungsten oxide, a tantalum oxide, a zincoxide, a titanium oxide, a tin oxide, a barium-zirconium compositeoxide, a silicon nitride, a silicon oxynitride, a zirconium silicate,and a hafnium silicate.

The substrate 110 may be a flexible substrate, which may include asurface layer having a hydroxyl (—OH) functional group. The flexiblesubstrate may include one or a mixture of two or more selected from thegroup including polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene(PP), triacetyl cellulose (TAC), polyethersulfone (PES), andpolydimethylsiloxane (PDMS).

The linkers 120A may be organic monomolecules bonded to the surface ofthe substrate 110 through self-assembly. The nano structure may includea linker layer 120 formed of a plurality of the linkers 120A bonded tothe surface of the substrate 110. The linker layer 120 may be aself-assembled monomolecular layer formed to be self-combined with thesurface of the substrate 110. Also, the linker layer 120 may be a silanecompound layer having one functional group selected from the groupincluding an amine group, a carboxylic acid group, and a thiol group.The linkers 120A may include one functional group selected from thegroup including an amine group, a carboxylic acid group, and a thiolgroup. Each of the linkers 120A may include a first functional group(which is denoted by 122 in FIG. 1B) bonded to the surface of thesubstrate 110, a second functional group (which is denoted by 126 inFIG. 1B) bonded to metal ions, and a chain group (which is denoted by124 in FIG. 1B) for connecting the first functional group and the secondfunctional group to each other.

The metallic nanoparticles 140 may be selected from the group includingmetal nanoparticles, metal oxide nanoparticles, metal nitridenanoparticles, metal carbide nanoparticles, and intermetallic compoundnanoparticles. The metallic nanoparticles 140 may be grown by bondingmetal ions to the linkers 120A and then growing the metallicnanoparticles 140.

The size of the metallic nanoparticles 140 may be controlled accordingto the energy application conditions while the metallic nanoparticles140 are grown. Also, the size of nanoparticles may be controlled beforethe energy for growing the metallic nanoparticles 140 is applied or inthe middle of applying the energy by whether a surfactant is supplied.The surfactant may be an organic surfactant, and the surfactant mayremain on the surface of the metallic nanoparticles 140 after thegrowing of the metallic nanoparticles 140 is finished. According to anembodiment of the present disclosure, when no surfactant is used, themetallic nanoparticles 140 may have a particle diameter of about 2.0 to3.0 nm. According to another embodiment of the present disclosure, whena single kind of surfactant is used, the metallic nanoparticles 140 mayhave a particle diameter of about 1.3 to 1.6 nm. According to anotherembodiment of the present disclosure, when a plurality of surfactants ofdifferent kinds are used, the metallic nanoparticles 140 may have aparticle diameter of about 0.5 to 1.2 nm.

The dielectric organic material 150 may be bonded to the surface of thegrown metallic nanoparticles 140. The dielectric organic material 150may prevent current from flowing through the metallic nanoparticles 140.The surface of the metallic nanoparticles 140 may be coated with thedielectric organic material 150, and the dielectric organic material 150may fill the space between the metallic nanoparticles 140 that arearranged apart from each other. When a surfactant is supplied to themetal ions before the metallic nanoparticles 140 are grown, or while thenanoparticles are growing, the surfactant may remain on the surface ofthe metallic nanoparticles 140. Since the surfactant may be a dielectricorganic material, if the arranged nanoparticles are insulative to eachother by the surfactant remaining after the nanoparticles are grown, thedielectric organic material 150 does not have to be further applied tothe nanoparticles after they are grown.

Although not illustrated in the drawing, an additional dielectricmaterial may be formed between the metallic nanoparticles 140 that arecoated with the dielectric organic material 150. In other words, whilethe dielectric organic material 150 is formed, an inorganic oxidematerial may be additionally formed in order to more stably fix themetallic nanoparticles 140. Also, an inorganic oxide material may beformed directly without the dielectric organic material 150.

The metallic nanoparticles 140 may be arranged spaced apart from eachother over the linker layer 120 to form a monomolecular nanoparticlelayer. The nanoparticle layer may include a dielectric material bondedto the surface of the metallic nanoparticles 140. The dielectricmaterial may include at least one from a group including an organicsurfactant, a dielectric organic material, and an inorganic oxide.

The nano structure in accordance with the first embodiment of thepresent disclosure may have a vertical multi-stack structure. In otherwords, the nano structure may have a stacked structure where the linkerlayer 120 and the nanoparticle layer are stacked alternately andrepeatedly. A dielectric layer capable of being bonded to the linkers ofthe upper linker layer may be further included. If a dielectric materialforming the lower nanoparticle layer has a functional group capable ofbeing bonded to the linkers of the upper linker layer, it does not haveto form the dielectric layer between the lower nanoparticle layer andthe upper linker layer. In short, whether to form the dielectric layerbetween the lower nanoparticle layer and the upper linker layer may bedecided based on the kind of the dielectric material that forms thenanoparticle layer.

Nano Structure and Fabrication Method Thereof in Accordance with aSecond Embodiment of the Present Invention

FIGS. 2A to 2E are cross-sectional views describing a nano structure anda method for fabricating the nano structure in accordance with a secondembodiment of the present disclosure.

The method for fabricating the nano structure in accordance with thesecond embodiment of the present disclosure may include preparing asubstrate 210 (refer to FIG. 2A), forming dielectric particle supporters222 where linkers 224 are bonded on the substrate 210 (refer to FIG.2B), bonding metal ions 230 to the linkers 224 (refer to FIG. 2C), andchanging (i.e. forming, reducing, or growing) the metal ions 230 intometallic nanoparticles 240 by applying energy to the metallicnanoparticles 240 (refer to FIG. 2D). The method may further includesupplying a dielectric organic material to the structure where themetallic nanoparticles 240 are formed (refer to FIG. 2E). Also, themethod may further include supplying one or a plurality of organicsurfactants before the energy is applied or during the application ofenergy.

FIG. 2A shows the substrate 210 prepared. The substrate 210 may have asurface layer 214. For example, the substrate 210 may be a siliconsubstrate 212 having an oxide layer as the surface layer 214.

The substrate 210 may be a flexible substrate or a transparentsubstrate. When a flexible substrate 210 is used, the surface layer 214may be an organic material having a hydroxyl (—OH) functional group.

Non-limiting examples of the flexible substrate include one or a mixtureof two or more selected from the group including polyethyleneterephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI),polycarbonate (PC), polypropylene (PP), triacetyl cellulose (TAC),polyethersulfone (PES), and polydimethylsiloxane (PDMS). Non-limitingexamples of the transparent substrate include a glass substrate and atransparent plastic substrate.

The substrate 210 may be a structure where all or part the constituentelements of an application device are already formed. The substrate 210may be a wafer, a film, or a thin film, and the surface of the substrate210 may be nano-patterned (structuralized) in consideration of thephysical shape of the application device that is designed along with atransistor having a recess structure or a three-dimensional structure.

In the second embodiment of the present disclosure, the substrate 210may have the materials and structures described in reference to thefirst embodiment of the present disclosure, and for the sake of brevitythey will not be described again.

FIG. 2B shows the dielectric particle supporters 222 where the linkers224 are bonded. The dielectric particle supporters 222 where the linkers224 are bonded may form a supporter layer 220.

A method for forming the supporter layer 220 where the linkers 224 arebonded over the substrate 210 may include preparing a supporter layermaterial by mixing a dielectric material in a linker solution obtainedby dissolving the linkers 224 in a solvent, and depositing the supporterlayer material on the substrate 210. The supporter layer material may beapplied on the substrate 210 using a spin-coating method, or a liquiddeposition method of immersing the substrate 210 in a solution where thesupporter layer material is dissolved may be used.

The dielectric particle supporters 222 may include an oxide having atleast one element selected from the group including metals, transitionmetals, post-transition metals, and metalloids. Also, the dielectricparticle supporters 222 may include at least one material selected fromthe group including a silicon oxide, a hafnium oxide, an aluminum oxide,a zirconium oxide, a barium-titanium composite oxide, an yttrium oxide,a tungsten oxide, a tantalum oxide, a zinc oxide, a titanium oxide, atin oxide, a barium-zirconium composite oxide, a silicon nitride, asilicon oxynitride, a zirconium silicate, a hafnium silicate andpolymers.

The linkers 224 may be organic monomolecules that are capable of beingchemically bonded to or adsorbed on the surface of the dielectricparticle supporters 222 and of being chemically bonded to the metal ions230. To be specific, the linkers 224 may be organic monomolecules thatinclude a first functional group capable of being chemically bonded toor adsorbed on the surface of the dielectric particle supporters 222 anda second functional group capable of being chemically bonded to metalions, which are to be formed subsequently. The linkers 224 may alsoinclude a chain functional group 124 for connecting the first functionalgroup and the second functional group to each other. The linkers 224 mayinclude one functional group capable of being bonded to metal ions whichis selected from the group including an amine group, a carboxylic acidgroup, and a thiol group. The linkers 224 may be formed of the same orsimilar materials through diverse methods as described in reference tothe first embodiment of the present disclosure.

FIG. 2C shows metal ions 230 bonded to the linkers 224. The metal ions230 may be bonded to the functional groups of the linkers 224. The metalions 230 may be formed by supplying a metal precursor to the substrate(having the linkers formed thereon). Specifically, the metal ions 230may be formed by applying a metal precursor solution to the substrate210 or by applying a gaseous metal precursor to the substrate 210. Inthe second embodiment of the present disclosure, the method for bondingthe metal ions 230 to the linkers 224 and the materials used for themethod may be as diverse as in the description of the first embodimentof the present disclosure.

FIG. 2D shows metallic nanoparticles 240 formed by applying energy andgrowing the metal ions 230. The energy that is applied to form thenanoparticles may be one or more selected from among heat energy,chemical energy, light energy, vibration energy, ion beam energy,electron beam energy, and radiation energy. The diverse embodiments maybe the same as or similar to those of the first embodiment of thepresent disclosure.

In a fabrication method according to a second embodiment of the presentdisclosure, i) the size of nanoparticles may be controlled by supplyingan organic surfactant that is to be bonded to or adsorbed on the metalions, followed by application of energy. Otherwise, ii) the size ofnanoparticles may be controlled daring the growth thereof by supplyingan organic surfactant that is to be bonded to or adsorbed on the metalions during application of energy. This supply of the organic surfactantmay be optionally performed during the fabrication process. As theorganic surfactant that is applied before or during application ofenergy, one or more kinds of organic surfactants may be used.

To more effectively inhibit the transfer of the metal ions, a firstorganic material and a second organic material of different kinds may beused as the surfactants.

The first organic material may be a nitrogen- or sulfur-containingorganic compound. For example, the sulfur-containing organic materialmay include a linear or branched hydrocarbon compound having a thiolgroup at one end. In a specific example, the sulfur-containing organiccompound may be one or more selected from a group including HS—C_(n)—CH₃(n: an integer ranging from 2 to 20), n-dodecyl mercaptan, methylmercaptan, ethyl mercaptan, butyl mercaptan, ethylhexyl mercaptan,isooctyl mercaptan, tert-dodecyl mercaptan, thioglycolacetic acid,mercaptopropionic acid, mercaptoethanol, mercaptopropanol,mercaptobutanol, mercaptohexanol and octyl thioglycolate.

The second organic material may be a phase-transfer catalyst-basedorganic compound, for example, quaternary ammonium or a phosphoniumsalt. More specifically, the second organic surfactant may be one ormore selected from a group including tetraocylyammonium bromide,tetraethylammonium, tetra-n-butylammonium bromide, tetramethylammoniumchloride, and tetrabutylammonium fluoride.

FIG. 2E shows a dielectric organic material 250 bonded to the metallicnanoparticles 240 grown by application of energy. The dielectric organicmaterial 250 may be in a state in which it coats the surface of themetallic nanoparticles 240 or fills the gaps between the metallicnanoparticles 240. The dielectric organic material 250 may provideisolation between the nanoparticles to more reliably prevent the flow ofcurrent between nanoparticles.

If a sufficient amount of the organic surfactant was supplied in thepreceding action, that is, if the organic surfactant that is appliedbefore or during application of energy remains on the surface of thegrown nanoparticles to provide sufficient isolation between the grownnanoparticles, further dielectric organic material 250 may not need tobe added to the surface of the grown nanoparticles 240. In other words,because whether the organic surfactant is to be used or not isdetermined according to the size of nanoparticles to be formed, step offorming the dielectric organic material 250 after the formation of thenanoparticles 240 is optional.

In the second embodiment of the present disclosure, the method forforming the dielectric organic material 250 and the materials used forthe method may be the same as or similar to those of the firstembodiment of the present disclosure.

Referring to FIG. 2E, the nano structure formed through the fabricationmethod in accordance with the second embodiment of the present inventionis described in detail.

Referring to FIG. 2E, the nano structure in accordance with the secondembodiment of the present invention may include a substrate 210,dielectric particle supporters 222 where the linkers 224 are bondedformed over the substrate 210, and metallic nanoparticles 240 that aregrown from metal ions bonded to the linkers 224. Also, the nanostructure may further include a dielectric organic material 250 having afunctional group bonded to the surface of the metallic nanoparticles240.

The substrate 210 may include a surface layer 214. The surface layer 214may include an oxide layer. To be specific, non-limiting examples of thesurface layer 214 of the substrate 210 may be a layer of at least onematerial selected from the group including a silicon oxide, a hafniumoxide, an aluminum oxide, a zirconium oxide, a barium-titanium compositeoxide, an yttrium oxide, a tungsten oxide, a tantalum oxide, a zincoxide, a titanium oxide, a tin oxide, a barium-zirconium compositeoxide, a silicon nitride, a silicon oxynitride, a zirconium silicate,and a hafnium silicate.

The substrate 210 may be a flexible substrate, which may include asurface layer having a hydroxyl (—OH) functional group. The flexiblesubstrate may include one or a mixture of two or more selected from thegroup including polyethylene terephthalate (PET), polyethylenenaphthalate (PEN), polyimide (PI), polycarbonate (PC), polypropylene(PP), triacetyl cellulose (TAC), polyethersulfone (PES), andpolydimethylsiloxane (PDMS).

The dielectric particle supporters 222 may be oxide particles includingat least one element selected from the group including metals,transition metals, post-transition metals, and metalloids. Thedielectric particle supporters 222 may be particles having an averageparticle diameter of about 10 to 20 nm. The dielectric particlesupporters 222 may be formed as a monomolecular layer or a polymolecularlayer over the substrate 210.

Also, the dielectric particle supporters 222 may include at least onematerial selected from the group including a silicon oxide, a hafniumoxide, an aluminum oxide, a zirconium oxide, a barium-titanium compositeoxide, an yttrium oxide, a tungsten oxide, a tantalum oxide, a zincoxide, a titanium oxide, a tin oxide, a barium-zirconium compositeoxide, a silicon nitride, a silicon oxynitride, a zirconium silicate, ahafnium silicate and polymers.

The linkers 224 may be organic monomolecules. The nano structure mayinclude a linker layer formed of the plurality of the linkers 224 bondedto the surface of the substrate 210. The linker layer may be aself-assembled monomolecular layer formed to be self-combined with thesurface of the dielectric particle supporters 222. The linkers 224 mayinclude one functional group selected from the group including an aminegroup, a carboxylic acid group, and a thiol group. The linkers 224 mayinclude first functional groups bonded to the surface of the dielectricparticle supporters 222, second functional groups bonded to metal ions,and chain groups for connecting the first functional groups and thesecond functional groups to each other.

The metallic nanoparticles 240 may be selected from the group includingmetal nanoparticles, metal oxide nanoparticles, metal nitridenanoparticles, metal carbide nanoparticles, and intermetallic compoundnanoparticles. The metallic nanoparticles 240 may be grown by bondingmetal ions to the linkers 224 and then growing the metal ions.

The size of the metallic nanoparticles 240 may be controlled accordingto the energy application conditions while the metallic nanoparticles240 are grown. Also, the size of nanoparticles may be controlled beforethe energy for growing the metallic nanoparticles 240 is applied orduring energy application by whether a surfactant is supplied. Thesurfactant may be an organic surfactant, and the surfactant may remainon the surface of the metallic nanoparticles 240 after the growing ofthe metallic nanoparticles 240 is finished. According to an embodimentof the present disclosure, when no surfactant is used, the metallicnanoparticles 240 may have a particle diameter of about 2.0 to 3.0 nm.According to another embodiment of the present disclosure, when a singlekind of surfactant is used, the metallic nanoparticles 240 may have aparticle diameter of about 1.3 to 1.6 nm. According to anotherembodiment of the present disclosure, when a plurality of differentkinds of surfactants is used, the metallic nanoparticles 240 may have aparticle diameter of about 0.5 to 1.2 nm.

The dielectric organic material 250 may be bonded to the surface of thegrown metallic nanoparticles 240. The dielectric organic material 250may prevent current from flowing through the metallic nanoparticles 240.The surface of the metallic nanoparticles 240 may be coated with thedielectric organic material 250, and the dielectric organic material 250may fill the space between the metallic nanoparticles 240 that arespaced apart from each other. When a surfactant is supplied to the metalions, which are the state of the metallic nanoparticles 240 before themetallic nanoparticles 240 are grown, or while the nanoparticles arebeing grown, the surfactant may remain on the surface of the metallicnanoparticles 240. Since the surfactant may be a dielectric organicmaterial as well, if the arranged nanoparticles are insulative to eachother simply by the surfactant remaining after the nanoparticles aregrown, further application of dielectric organic material 250 after thenanoparticles are grown may be unnecessary.

Although not illustrated in the drawing, a dielectric material may beadditionally formed between the metallic nanoparticles 240 that arecoated with the dielectric organic material 250. In other words, inaddition to the dielectric organic material 250 being formed, aninorganic oxide material may be additionally formed in order to morestably fix the metallic nanoparticles 240. Also, an inorganic oxidematerial may be formed directly without the dielectric organic material250.

The metallic nanoparticles 240 may be spaced apart from each other toform a monomolecular nanoparticle layer. The nanoparticle layer mayinclude a dielectric organic material (or an organic material for asurfactant) bonded to or coating the surface of the metallicnanoparticles 240. The nanoparticle layer may further include aninorganic oxide material that fills the gaps between the coatednanoparticles 240.

The nano structure in accordance with the second embodiment of thepresent disclosure may have a vertical multi-stack structure. In otherwords, the nano structure may have a stacked structure where thesupporter layer 220, which is bonded to the linkers 224, and thenanoparticle layer are stacked alternately and repeatedly. A dielectriclayer having functional groups capable of being bonded to the dielectricparticle supporters 222 where the linkers 224 are bonded, may be furtherincluded between the lower nanoparticle layer and the upper supporterlayer. If the dielectric organic material 250 forming the lowernanoparticle layer has functional groups capable of being bonded to theupper supporter layer, the forming of the additional dielectric layermay be unnecessary. In short, whether to form the dielectric layer maybe decided based on the kind of dielectric organic material 250 that isapplied.

According to the embodiments of the present invention, the nanostructures are extremely fine, have uniform size, and may be fabricatedin high density. Also, since the nanoparticles are fixed by dielectriclinkers, the nano structures have excellent physical stability. Forthese reasons, an application device using the nano structures may beeasily scaled, and while the application device is scaled, theapplication device still retains excellent operation stability,reproducibility, and reliability.

According to the embodiments of the present invention, the nanostructures may be fabricated through an in-situ process. Therefore,production cost may be minimized, and mass-production within a shorttime may be possible.

The nano structures and fabrication methods thereof in accordance withthe embodiments of the present disclosure may have nanoparticle sizescontrolled through a simple process of using a surfactant and inducing areaction during the growth of the nanoparticles. In short, thenanoparticles may be prepared in a desired particle size, while securingthe characteristics of an application device.

Although various embodiments have been described for illustrativepurposes, it will be apparent to those skilled in the art that variouschanges and modifications may be made without departing from the spiritand scope of the disclosure as defined in the following claims.

What is claimed is:
 1. A method for fabricating a nano structure,comprising: forming a substrate; forming linkers over the substrate;forming metal ions over the linkers; and aggregating the metal ions,each of which is bonded to the substrate through each of the linkers, toeach other to form one or more metallic nanoparticles, wherein each ofthe metallic nanoparticles is formed by aggregating between one metalion bonded to one linker and another metal ion bonded to another linker.2. The method of claim 1, wherein the forming of the metal ions over thelinkers includes: bonding the metal ions to the linkers.
 3. The methodof claim 2, wherein the forming of one or more metallic nanoparticlesfurther includes: growing the metal ions bonded to the linkers.
 4. Themethod of claim 3, wherein the forming of one or more metallicnanoparticles includes: applying energy to the metal ions.
 5. The methodof claim 4, wherein the energy is at least one selected from the groupconsisting of heat energy, chemical energy, light energy, vibrationenergy, ion beam energy, electron beam energy, and radiation energy. 6.The method of claim 4, wherein the metallic nanoparticles are formed ofone selected from the group consisting of metal nanoparticles, metaloxide nanoparticles, metal nitride nanoparticles, metal carbidenanoparticles, and intermetallic compound nanoparticles, by supplying adifferent type of material than the metal ions during the application ofenergy to the metal ions.
 7. The method of claim 4, wherein the energyis simultaneously applied to all metal ion-bonded regions.
 8. The methodof claim 4, wherein the energy is selectively or intermittently appliedto keep a portion of the metal ions from being particlized.
 9. Themethod of claim 3, further comprising: bonding at least one of adielectric organic material and an inorganic oxide to a surface of themetallic nanoparticles.
 10. The method of claim 3, further comprising:supplying an organic surfactant of one or more kinds before or duringthe forming of one or more metallic nanoparticles.
 11. The method ofclaim 10, wherein the organic surfactant is a nitrogen-containingorganic material or a sulfur-containing organic material.
 12. The methodof claim 10, wherein the organic surfactant includes a first organicmaterial and a second organic material of different kinds, wherein thefirst organic material is a nitrogen-containing organic material or asulfur-containing organic material, and wherein the second organicmaterial is a phase-transfer catalyst-based organic material.
 13. Themethod of claim 3, wherein the linkers are organic monomolecules, andwherein the forming of the linkers includes: preparing a linkersolution; and forming a self-assembled monomolecular layer by applyingthe linker solution to a surface of the substrate.
 14. The method ofclaim 3, wherein the linkers are formed through an Atomic LayerDeposition (ALD) process using a gas containing the linkers.
 15. Themethod of claim 14, wherein the forming of the linkers includes: forminga silane compound layer through an Atomic Layer Deposition (ALD)process.
 16. The method of claim 3, wherein the linkers include at leastone functional group selected from the group consisting of an aminegroup, a carboxyl group, and a thiol group, to be bonded to the metalions.
 17. The method of claim 3, wherein the bonding of the metal ionsto the linkers includes: applying a metal precursor to the linkers. 18.The method of claim 3, wherein the bonding of the metal ions to thelinkers includes: applying a metal precursor solution to a structurewhere the linkers are bonded, or supplying a gas-phase metal precursorto the structure where the linkers are bonded.
 19. The method of claim3, wherein the forming of the substrate includes: forming a surfacelayer capable of bonding the linkers on a surface of the substrate. 20.The method of claim 19, wherein the surface layer is formed of one ormore selected from the group consisting of metals, metal oxides,semiconductors and semiconductor oxides.
 21. The method of claim 4,wherein the application of energy is adjusted to control a size ordensity of the metallic nanoparticles.